Computational and Theoretical Chemistry最新文献

{"title":"Novel cyclic BxCyHz nanorings: First-principles design and electronic tunability of unexplored boron–carbon hybrid nanostructures","authors":"Ketlen Brenda de O. Rodrigues ,&nbsp;Isaac M. Virgilio ,&nbsp;David L. Azevedo","doi":"10.1016/j.comptc.2026.115688","DOIUrl":"10.1016/j.comptc.2026.115688","url":null,"abstract":"<div><div>This study investigates cyclic boron–carbon–hydrogen (B<span><math><msub><mrow></mrow><mrow><mi>x</mi></mrow></msub></math></span>C<span><math><msub><mrow></mrow><mrow><mi>y</mi></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mi>z</mi></mrow></msub></math></span>) isomers to assess their structural stability and potential as functional materials. A systematic enumeration satisfying <span><math><mrow><mi>x</mi><mo>+</mo><mi>y</mi><mo>=</mo><mn>6</mn></mrow></math></span> yields 64 distinct structures. Electronic, thermodynamic, and optical properties were evaluated using density functional theory (DFT) at the GGA-PBE level, with vibrational analyses refined using the HSE06 hybrid functional. Energetic screening identifies 12 dynamically stable isomers with binding energies between <span><math><mrow><mo>−</mo><mn>0</mn><mo>.</mo><mn>34</mn></mrow></math></span> and <span><math><mrow><mo>−</mo><mn>0</mn><mo>.</mo><mn>16</mn></mrow></math></span> eV/atom and no imaginary frequencies. Band gaps span 0.399–5.169 eV (GGA-PBE) and 0.761–6.238 eV (HSE06), indicating broad electronic tunability. Gibbs free energy calculations using borane (BH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>) and ethylene (C<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>) as precursors show favorable formation energetics (<span><math><mrow><mi>Δ</mi><mi>G</mi><mo>&lt;</mo><mn>0</mn></mrow></math></span>) over 298–1000 K. Optical absorption extends from visible to ultraviolet (173–1527 nm). These results demonstrate that compositional variation enables systematic tuning of nanoring properties, supporting their potential for electronic, optical, and biomedical applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115688"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The limits of low-spin zinc oxidation states from density functional theory computations: Fluoro‑zinc complexes, [ZnFn]x, where n = 1 through 6 and x = 2+ through 3-, including complexes containing the η1-F2-, 1-η1-F3-, and 1,3-η2-F3-ligands","authors":"Lowen M. Hobbs,&nbsp;Hanna D. Hobbs,&nbsp;Robert W. Zoellner","doi":"10.1016/j.comptc.2026.115707","DOIUrl":"10.1016/j.comptc.2026.115707","url":null,"abstract":"<div><div>Density functional theory calculations, at the ωB97X-D/6‐311+G* level of theory, were performed on singlet and doublet spin state fluoro‐zinc complexes [ZnF_<em>n</em>]^<em>x</em>, where <em>n</em> = 1 through 6 and <em>x</em> = 2+ through 3-, to determine the highest positive and lowest negative zinc oxidation states that could be supported in these complexes. All fluoro‐zinc stoichiometries stabilized zinc(III) and zinc(II). The highest positive zinc oxidation state was in the [Zn^VIIF₅]²⁺ square pyramidal and trigonal bipyramidal complexes. Oxidation states as negative as zinc(0) in the bent [Zn⁰F₂]²^‐ and zinc(<img>I) in the [Zn^-IF]²^‐ complexes were also observed. No singlet or doublet fluoro‐‑zinc complexes with charges more positive than 2+, or more negative than 3-, could be optimized. However, complexes which contained the η¹-F₂ ligand were discovered, <em>e.g.</em>, the triskelion-shaped [Zn^II(η¹-F₂)₃]²⁺, and complexes containing the η¹⁾-F₃- and 1,3-η²-F₃ ligands were also identified.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115707"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A molecular dynamics simulation study on the salt tolerance of saturated cardanol surfactants in a crude oil-water system","authors":"Congying Lu ,&nbsp;Zhenyu Yuan ,&nbsp;Xinyi Xu ,&nbsp;Jianguang Wei ,&nbsp;Xiaofeng Zhou ,&nbsp;Shamil Sultanov ,&nbsp;Limin Li ,&nbsp;Huijuan Qian ,&nbsp;Qinghe Gao ,&nbsp;Wei Ding","doi":"10.1016/j.comptc.2026.115697","DOIUrl":"10.1016/j.comptc.2026.115697","url":null,"abstract":"<div><div>In oilfield exploitation, formation water typically contains high concentrations of inorganic salts such as NaCl and CaCl₂, which can diminish the effectiveness of conventional surfactants and potentially render them ineffective. This study focuses on nonionic and anionic–nonionic surfactants derived from cardanol and the synergistic mechanism between inorganic salts and surfactants in reducing oil–water interfacial tension is elucidated. The results indicate that within a specific concentration range (0.2–1.2 mol/L), both NaCl and CaCl₂ can improve the interfacial performance of surfactants and effectively lower interfacial tension. The extent of reduction follows the order: 8EO8POC2SO₃ (sulfonate) &gt; 8EO8POSO₃ (sulfate) &gt; 8EO8POH (nonionic surfactant), CaCl₂ &gt; NaCl. These findings suggest that by selecting appropriate types and concentrations of inorganic salt ions, the interfacial tension of the crude oil–water system can be reduced synergistically.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115697"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nature and energetics of a prototypical ultra-weak type I Cl···Cl interaction: A multi-method computational study","authors":"Melek Hajji","doi":"10.1016/j.comptc.2026.115714","DOIUrl":"10.1016/j.comptc.2026.115714","url":null,"abstract":"<div><div>Halogen···halogen interactions are subtle noncovalent contacts that influence crystal packing and molecular assembly, yet the physical nature and energetics of nondirectional Type I contacts remain an active area of research. Here, a comprehensive multi-method quantum chemical study is reported for a prototypical Type I C–Cl···Cl–C interaction, identified within a crystal-extracted homodimer of dichloro-dimethoxy biphenyl compound. Dispersion-corrected DFT (PW6B95-D3/aug-cc-pVTZ), molecular electrostatic potential (MEP), real-space topology (QTAIM, ELF, IGMH, and IRI), natural bond orbital (NBO) analysis, and symmetry-adapted perturbation theory (SAPT) were employed. The interaction is attractive but ultra-weak (−0.27 kcal mol⁻¹), with London dispersion dominating the stabilization (≈69%). Electrostatic contributions are negligible, and reciprocal LP(Cl) → σ*(C<img>Cl) donor–acceptor delocalizations are marginal (total E⁽²⁾ = 0.60 kcal mol⁻¹). MEP analysis proved inadequate for describing this contact, as the σ-hole exhibited clear sensitivity to the chosen isodensity surface and level of theory. Topological analyses provide both visual and quantitative confirmation of a well-defined, closed-shell, van der Waals-type interaction; the associated bond path follows diffuse chlorine lone-pair tails, consistent with the side-on Type I conformation. Beyond this specific case, this work establishes a practical methodological framework for a deeper electronic understanding of similar weak halogen···halogen interactions that complements purely geometric criteria.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115714"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185873","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electronic and structural modulation of the B- and N-doped phenine nanotubes","authors":"Aercio F.F. De F. Pereira,&nbsp;Puspitapallab Chaudhuri,&nbsp;Angsula Ghosh","doi":"10.1016/j.comptc.2026.115698","DOIUrl":"10.1016/j.comptc.2026.115698","url":null,"abstract":"<div><div>Phenine nanotubes (pNTs), constructed from benzene rings, form a new class of porous carbon-based nanostructures with highly tunable structural and electronic features. The influence of boron–nitrogen (BN) substitution and hydrogen depletion on pNT geometry and electronic behavior is investigated across ten configurations, including pristine, single-element (B or N), and mixed B–N substitutions arranged symmetrically and asymmetrically. Among the doped systems, the hydrogenated nitrogen-substituted pNT is the most stable. BN incorporation preserves the tubular framework while subtly reshaping pore size and morphology. Both doping and hydrogenation allow controlled modulation of pore geometry. Hydrogen removal in pristine pNTs induces a semiconductor-to-metal transition, whereas hydrogen-depleted single-element substitutions lead to significant band-gap widening. In contrast, hydrogenated mixed B–N systems show strong gap suppression, often eliminating the bandgap entirely. The combined tunability in porosity and electronic response positions BN-substituted pNTs as promising candidates for future nanoelectronic and sensing technologies.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115698"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185522","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Regulatory mechanism of inorganic fillers on Zn2+ transport in PEO–Zn(TFSI)2 electrolyte within all-solid-state zinc-ion batteries","authors":"Yong Wang ,&nbsp;Yufeng Yang ,&nbsp;Wolong Li ,&nbsp;Yongcun Li","doi":"10.1016/j.comptc.2026.115684","DOIUrl":"10.1016/j.comptc.2026.115684","url":null,"abstract":"<div><div>All-solid-state zinc-ion batteries (ZIBs) require electrolytes that deliver both high ionic conductivity and high safety; however, the Zn²⁺ migration mechanisms in composite solid electrolytes remain unclear. In this work, we combine molecular dynamics (MD) simulations with density functional theory (DFT) calculations to study Zn²⁺ transport in a PEO-Zn(TFSI)₂ matrix and in its composites containing SiO₂, ZnPS₃, and a ZnPS₃/MoS₂ hybrid filler, with a particular focus on bulk plasticization and interfacial transport pathways. The results show that SiO₂ delivers a modest low-temperature gain primarily by reducing crystallinity. ZnPS₃ weakens Zn<img>O coordination while forming a Zn-P-dominated interfacial network and a space-charge layer, thereby enhancing diffusion across a broad temperature window. Surface states on ZnPS₃(001) induce electron accumulation that electrostatically drives Zn²⁺ enrichment at the interface. The introduction of MoS₂ further enhances the interfacial dipole and geometric connectivity, resulting in a relative increase of approximately 1.5–2.4 times in the MSD slope at medium-to-high temperatures compared to PEO + ZnPS₃. MD and DFT calculations demonstrate that the synergistic effect of chemically driven coordination exchange and geometrically guided epitaxial channels substantially enhances zinc ion mobility within the electrolyte.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115684"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076753","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantum information geometry meets DMRG: Uhlmann gauge improvements in computational methods","authors":"Andrei T. Patrascu","doi":"10.1016/j.comptc.2025.115623","DOIUrl":"10.1016/j.comptc.2025.115623","url":null,"abstract":"<div><div>Standard DMRG truncation based purely on singular values can induce unphysical discontinuities along path parameters such as sweeps or molecular geometries, particularly near avoided crossings and quasi-degeneracies. We formulate a dynamical Uhlmann gauge on reduced density matrices along such paths, and use the induced covariant derivatives and curvatures to define continuity-aware truncation scores that are both gauge invariant and purification independent. On a gapped spin-chain benchmark, the resulting Uhlmann-guided DMRG preserves the variational optimum and non-parallelity error at fixed bond dimension <span><math><mi>M</mi></math></span> while producing much smoother entanglement spectra and overlaps. As a simple chemistry-relevant proof of principle, we also analyse a small-CAS LiF potential-energy scan at the reduced-density level and show that the Uhlmann-based selection strongly suppresses pathological Schmidt-subspace rotations along the bond coordinate. The method therefore provides a principled continuity prior that complements conventional SVD-based truncation and improves path smoothness of gauge-sensitive quantities without altering physical observables.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115623"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Benchmarking DFT methods for calculating reorganization energies in charge transport properties of organic semiconductors: A case study of nitro-aniline molecules","authors":"Emmanuel Madakobiyé ,&nbsp;Marius Bouba Ousmanou ,&nbsp;Fridolin Tchangnwa Nya ,&nbsp;Geh Wilson Ejuh ,&nbsp;Alhadji Malloum ,&nbsp;Jeanet Conradie","doi":"10.1016/j.comptc.2026.115664","DOIUrl":"10.1016/j.comptc.2026.115664","url":null,"abstract":"<div><div>Due to its occurrence in the exponential term of the Marcus–Hush hopping rate equation, precise prediction of the internal reorganization energy (<span><math><msub><mrow><mi>λ</mi></mrow><mrow><mtext>int</mtext></mrow></msub></math></span>) is essential for reliable modeling of charge carrier mobility (<span><math><mi>μ</mi></math></span>) in organic semiconductors. In this work, we calculated both hole (<span><math><msub><mrow><mi>λ</mi></mrow><mrow><mtext>h</mtext></mrow></msub></math></span>) and electron (<span><math><msub><mrow><mi>λ</mi></mrow><mrow><mtext>e</mtext></mrow></msub></math></span>) reorganization energies across three nitro-aniline push–pull isomers (ONA, MNA, PNA) by methodically benchmarking eighteen Density Functional Theory (DFT) functionals against the gold standard CCSD(T)/6-311++G(d,p) reference data. To demonstrate quantitative agreement, performance was evaluated using standard metrics (MAD, RMSD) supplemented by correlation coefficients (<span><math><msup><mrow><mi>R</mi></mrow><mrow><mn>2</mn></mrow></msup></math></span>). According to the analysis, double hybrid functionals: rev-DSD-PBEP86-D3 and rev-DSD-PBEP86-D3BJ functionals perform better with a Mean Absolute Deviation (MADs) of roughly 0.23<!--> <!-->meV and a nearly perfect correlation with the CCSD(T) trend (<span><math><mrow><msup><mrow><mi>R</mi></mrow><mrow><mn>2</mn></mrow></msup><mo>&gt;</mo><mn>0</mn><mo>.</mo><mn>95</mn></mrow></math></span>). On the other hand, hybrid functionals like M06 and CAM-B3LYP demonstrated notable discrepancies for specific isomers, underscoring their restricted suitability for precise <span><math><mi>λ</mi></math></span> prediction. We recommend the rev-DSD-PBEP86-D3BJ methods as robust, less computationally demanding alternatives to CCSD(T) for these systems. This foundational work provides reliable DFT methods essential for subsequent accurate calculations of electronic coupling and charge transport mobilities, enabling future quantitative comparison with experimental data for nitro-aniline-like materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115664"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Inverse isotope effect in Pd: First-principles insights into hydrogen isotope diffusion, dissolution, and permeation","authors":"Ting Zhang,&nbsp;Jun Tang,&nbsp;Xiaoqiu Ye","doi":"10.1016/j.comptc.2026.115710","DOIUrl":"10.1016/j.comptc.2026.115710","url":null,"abstract":"<div><div>Utilizing first-principles calculations within the framework of density functional theory, this work systematically investigates the dissolution, diffusion, and permeation of hydrogen (H), deuterium (D), and tritium (T) in palladium. A key finding is the prediction of a distinct inverse isotope effect in diffusion at low temperatures (T &lt; ∼800 K), where the calculated diffusion coefficients increase with the mass of the isotope, contrary to classical expectations. This anomaly is quantitatively traced to the reduction of the effective diffusion barrier with increasing isotope mass due to zero-point energy contributions. In contrast, dissolution and permeation maintain the normal isotope trend. By integrating microscopic calculations with a macroscopic Fick transport model, this study offers crucial insights into the quantum-mechanical origins of isotope effects in metals and guides the design of Pd-based membranes for isotope separation applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115710"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational determination of pyrrolopyridine formation rates via the intramolecular inverse diels–alder reaction of pyrazine derivatives","authors":"Meryem Fıstıkçı ,&nbsp;Ferruh Lafzi ,&nbsp;Selçuk Eşsiz","doi":"10.1016/j.comptc.2026.115689","DOIUrl":"10.1016/j.comptc.2026.115689","url":null,"abstract":"<div><div>A systematic computational study of the intramolecular inverse electron-demand Diels-Alder (IEDDA) reactions of 2-aminopyrazine derivatives and following <em>retro</em>-Diels-Alder (<em>r</em>DA) reactions is disclosed, including an examination of the impact of N, C3 and C6 substituents. The computations are carried out employing DFT and high-level coupled-cluster methods. The IEDDA cycloaddition transition state exhibits the highest activation barrier and is therefore the rate-determining step. <em>N</em> substituents were found to exhibit a remarkable impact on the cycloaddition reactivity of the 2-aminopyrazine without altering, and even more enhancing, the intrinsic cycloaddition regioselectivity. Moreover, the study revealed that the reaction can be predictably modulated by a C3 or C6 substituent and portends extensive synthetic utility for a target pyrrolopyridine scaffolds.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1258 ","pages":"Article 115689"},"PeriodicalIF":3.0,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}